Redox-Controlled Reactivity at Boron: Parallels to Frustrated Lewis/Radical Pair Chemistry

Anthony Wong, Jiaxiang Chu, Guang Wu, Joshua Telser, Roman Dobrovetsky, Gabriel Menard*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

We report the synthesis of new Lewis-acidic boranes tethered to redox-active vanadium centers, (Ph2N)3V(μ-N)B(C6F5)2 (1a) and (N(CH2CH2N(C6F5))3)V(μ-N)B(C6F5)2 (1b). Redox control of the VIV/V couple resulted in switchable borane versus "hidden"boron radical reactivity, mimicking frustrated Lewis versus frustrated radical pair (FLP/FRP) chemistry, respectively. Whereas heterolytic FLP-type addition reactions were observed with the VV complex (1b) in the presence of a bulky phosphine, homolytic peroxide, or Snâ'hydride bond cleavage reactions were observed with the VIV complex, [CoCp2[[(N(CH2CH2N(C6F5))3)V(μ-N)B(C6F5)2] (3b), indicative of boron radical anion character. The extent of radical character was probed by spectroscopic and computational means. Together, these results demonstrate that control of the VIV/V oxidation states allows these compounds to access reactivity observed in both FLP and FRP chemistry.

Original languageEnglish
Pages (from-to)10343-10352
Number of pages10
JournalInorganic Chemistry
Volume59
Issue number14
DOIs
StatePublished - 20 Jul 2020
Externally publishedYes

Funding

FundersFunder number
National Science FoundationCHE-1900651, 1900651
American Chemical Society Petroleum Research Fund58693-DNI3
University of California, Santa Barbara
United States-Israel Binational Science Foundation2018221

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